Networked molecular cages as crystalline sponges for fullerenes and other guests
Networked molecular cages as crystalline sponges for fullerenes and other guests
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DOI：
10.1038/nchem.742
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发表时间：
2010-09-01
期刊：
影响因子：
21.8
通讯作者：
Fujita, Makoto
中科院分区：
文献类型：
--
作者：
Inokuma, Yasuhide;Arai, Tatsuhiko;Fujita, Makoto
许多分子笼在溶液中选择性地结合客人，但在固体状态下，紧密堆积经常阻止客人进入，这使得笼子不活跃。我们设想，由众所周知的分子笼构建的配位网络可以将丰富的溶液状态主-客体化学转化为固态。我们报道了一个由八面体M(6)L(4)笼形亚基(M=金属，L=配体)组成的无限阵列的晶体配位网络。这种配位网络是在分子水平上设计的“晶体分子海绵”，并保留了与溶液中发现的类似的客体识别特性。网络结晶度很强，因此X射线衍射分析可以用来明确地观察单晶到单晶的客体包裹体。空隙定义了交替的M(12)L(8)和M(12)L(24)立方八面体分子笼，这些大笼子通过简单地将晶体浸泡在富勒烯的甲苯溶液中，吸收高达35%的C(60)或C(70)的重量百分比。当晶体浸泡在富勒烯混合物中时，C(70)优先被吸收。
Many molecular cages selectively bind guests in solution, but in the solid state close packing often prevents guest entry, which renders the cages inactive. We envisioned that coordination networks constructed from well-known molecular cages could transfer the richness of solution-state host-guest chemistry into the solid state. We report a crystalline coordination network generated from an infinite array of octahedral M(6)L(4) cage subunits (M = metal, L = ligand). This coordination network is a 'crystalline molecular sponge' engineered on the molecular level and retains similar guest recognition properties to those found in solution. The network crystallinity is robust and thus X-ray diffraction analysis can be used to unambiguously observe single-crystal to single-crystal guest inclusion. The void spaces define alternating M(12)L(8) and M(12)L(24) cuboctahedral molecular cages and these large cages absorb up to 35 weight per cent of C(60) or C(70) by simply soaking the crystals in a toluene solution of the fullerene. When the crystals are immersed in fullerene mixtures, C(70) is preferentially absorbed.